Compositions, systems and methods using selective porous materials for oxygen separation

ABSTRACT

MOFs are disclosed that can efficiently adsorb oxygen from a gas stream, such as air. Systems and methods are also disclosed that utilize MOFs to separate oxygen from a gas stream. The separated oxygen may be used in a commercial process such as a combustion process.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to provisional patent applications U.S.Ser. No. 62/220,549, entitled “COMPOSITIONS, SYSTEMS AND METHODS FORSELECTIVE POROUS MATERIAL O2 SEPARATION,” by Nenoff et al., filed Sep.18, 2015, and provisional patent applications U.S. Ser. No. 62/325,833,entitled “COMPOSITIONS, SYSTEMS AND METHODS FOR SEPARATING OXYGEN FROMAIR AT AMBIENT TEMPERATURES,” by Nenoff et al., filed Apr. 21, 2016, thedisclosures of which is incorporated herein by reference in theirentireties.

GOVERNMENT RIGHTS

The Government has rights to this invention pursuant to Contract No.DE-AC04-94AL85000 awarded by the U.S. Department of Energy.

FIELD

The invention relates generally to gas separation and more particularlyto materials that selectively separate oxygen from air.

BACKGROUND OF THE INVENTION

Purified O₂ streams are utilized in many sectors of the industrialeconomy, including combustion, steel production, glass and cementproduction, petrochemical processing, metallurgy, pulp and paperproduction, and biochemical processing and waste treatment. For example,purified O₂ streams are used in oxy-fuel combustion to improve the heattransfer associated with stationary energy processes. In 2003, totalshipments of purified O₂ amounted to nearly 26 million tons, a value ofapproximately $1 billion, requiring over five million MWh of energy toproduce.

However, pure oxygen (O₂) generation's overall penetration intoindustrial and power markets is constrained by the high cost of existingair separation technologies. Cryogenic air separation is the most widelyused technology for generating large flows of oxygen but is a complexand expensive technology. Currently, for a 600 MWe (gross) oxy-fuelpower plant using cryogenic air separation, 100 MWe will be consumed byair-separation, resulting in an efficiency decrease of 10 percentagepoints. Pressure swing adsorption (PSA) is a competing technology thatuses separations materials such as activated carbon, zeolites andpolymer membranes. Current PSA technology is expensive and limited tomoderate purity O₂ applications because of limitations of existingseparations materials. For current zeolite-based PSA processes, capitalcosts (primarily adsorption vessels and compressors) and operating costs(primarily energy costs) each represent approximately 50% of the totalcost of air separation. There have been no significant breakthroughs inair separation technologies for several decades.

Technology is needed to reduce the expense and increase purity in O₂separation technology.

SUMMARY OF THE INVENTION

According to an embodiment of the disclosure, a composition is disclosedhaving the formula m/Cu-BTC, where BTC=benzene-1,3,5-tricarboxylic acidand m/Cu represents partial substitution of Cu with a metal ion (m)selected from a group consisting Sc, Ti, V, Mn, Fe and Co.

According to another embodiment of the disclosure, a process isdisclosed that includes contacting a gas stream containing oxygen at afirst concentration with a metal-organic framework material having theformula m/Cu-BTC, where BTC=benzene-1,3,5-tricarboxylic acid and m/Curepresents partial substitution of Cu with a metal ion (m) selected froma group consisting Sc, Ti, V, Mn, Fe and Co at a first temperature andfirst pressure to adsorb oxygen from the gas stream into themetal-organic framework, and desorbing oxygen from the metal-organicframework material at a second temperature and a second pressure.

According to another embodiment of the disclosure, a process isdisclosed that includes contacting a gas stream containing oxygen at afirst concentration with a metal-organic framework material having theformula m-(1,3,5-BTC), where BTC=Benzene-1,3,5-C₆H₃(CO₂H)₃, and wherem=Sc, Ti and V, at a first temperature and first pressure to adsorboxygen from the gas stream into the metal-organic framework; anddesorbing oxygen from the metal-organic framework material at a secondtemperature and a second pressure.

According to another embodiment of the disclosure, a process isdisclosed that includes contacting a gas stream containing oxygen at afirst concentration with a metal-organic framework material having theformula Eu(TTB)(DEF)(H₂O).(DEF)₅, where TTB is 3,3 0,4,4 0-tetra(trimethylsilylethynyl)biphenyl, and DEF is N,N′-diethylformamide at afirst temperature and first pressure to adsorb oxygen from the gasstream into the metal-organic framework; and desorbing oxygen from themetal-organic framework material at a second temperature and a secondpressure.

An object of the present disclosure is to disclose novel materialshaving improved O₂ sorption selectivity.

Another object of the present disclosure is to reduce the expense andincrease purity in O₂ separation technology by the use of highlyselective O2 adsorption materials to perform O₂ separations under mildconditions of low pressure and temperature.

Another object of the present disclosure is to disclose selectiveadsorption material-based separation technology, with improved capacityand competitive (or better) selectivity than zeolites, that dramaticallyreduce energy intensity, greenhouse gas footprint, and costs(anticipated reduction of 50%=2.5 million MWh of energy) over existingpurified O₂ streams.

Another object of the present disclosure is to utilize selectiveadsorption materials for gas separations at ambient pressure and roomtemperature, potentially revolutionizing the PSA process and providingdramatic process efficiency improvements through oxy-fuel combustion.

An advantage of the present disclosure is reduced expense and increasedpurity in O₂ separation technology.

Another advantage of the present disclosure is to reduce the CO₂ andenergy footprint of stationary energy production facilities.

Another advantage of the present disclosure is the use of materialshaving improved capacity and competitive (or better) selectivity thanzeolites, which will dramatically reduce energy intensity, greenhousegas footprint, and costs over existing purified O₂ streams, expandingthe market for non-cryogenic produced O₂.

Other objects, advantages and novel features, and further scope ofapplicability of the present invention will be set forth in part in thedetailed description to follow, taken in conjunction with theaccompanying drawings, and in part will become apparent to those skilledin the art upon examination of the following, or may be learned bypractice of the invention. The objects and advantages of the inventionmay be realized and attained by means of the instruments andcombinations particularly pointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a SEM image of a single crystal of SMOF-7.

FIG. 2 is a ball-and-stick representation of the Eu-dimetal clustermolecular building block.

FIG. 3 is a view of the framework in SMOF-7. Hydrogen atoms have beenomitted for clarity. Atom color scheme: Eu=lighter gray; N=white;C=darker gray; and O=black.

FIG. 4 illustrates novel (3,6)-connected net topography in SMOF-7. Thedimetal cluster is represented as octahedral node (grey), whereas theTTB linker is simplified as a 3-connected node (black).

FIG. 5 shows O₂ vs. N₂ sorption isotherm measured at 77 K in SMOF-7.

FIG. 6A shows O₂ and N₂ adsorption isotherms on Sc-MIL-100 measured at77 K.

FIG. 6B shows O₂ and N₂ adsorption isotherms on Sc-MIL-100 measured at258 K.

FIG. 6C shows O₂ and N₂ adsorption isotherms on Sc-MIL-100 measured at298 K.

FIG. 6D shows O₂ and N₂ adsorption isotherms on Sc-MIL-100 measured at313 K.

FIG. 6E shows O₂ and N₂ heats of adsorption derived from independentlyfitted virial isotherms at 258 K, 298 K, and 313 K, for the Sc-MIL-100sample.

FIG. 7A shows calculated (IAST) O₂/N₂ selectivity for a 20:80 O₂/N₂mixture from Sc-MIL-100 experimental isotherms measured at 258, 298, and313 K. (b)

FIG. 7B shows O₂ adsorption and desorption in Sc-MIL-100 over 10 cyclesat 298 K and 1 atm.

FIG. 8A shows O₂ and N₂ adsorption isotherms on Fe-MIL-100 measured at77 K.

FIG. 8B shows O₂ and N₂ adsorption isotherms on Fe-MIL-100 measured at258 K (the dashed line represents the independent fit to theexperimental data for each temperature using a modified virialequation).

FIG. 8C shows O₂ and N₂ adsorption isotherms on Fe-MIL-100 measured at298 K (the dashed line represents the independent fit to theexperimental data for each temperature using a modified virialequation).

FIG. 8D shows O₂ and N₂ adsorption isotherms on Fe-MIL-100 measured at313 K (the dashed line represents the independent fit to theexperimental data for each temperature using a modified virialequation).

FIG. 8E shows O₂ and N₂ heats of adsorption derived from independentlyfitted virial isotherms at 258, 298, and 313 K, for a Fe-MIL-100 sample.

FIG. 8F shows calculated (IAST) O₂/N₂ selectivity for a 20:80 O₂/N₂mixture from Fe-MIL-100 experimental isotherms measured at 258, 298, and313 K.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure is directed to new materials that have highselectivity for O₂ adsorption from a gas stream containing O₂. Thepresent disclosure is further directed to new processes for sorbing O₂from a gas stream containing O₂. In an embodiment, the gas stream may beair.

The new materials according to this disclosure include partiallysubstituted, activated Cu-BTC. Cu-BTC is also known as HKUST-1 orCu₂(BTC)₃, but will be referred to herein afterwards as Cu-BTC, whereBTC=benzene-1,3,5-tricarboxylic acid. The partially substituted,activated Cu-BTC (represented by m/Cu-BTC) may be partially substitutedby one or more metals selected from a group including Sc, Ti, V, Mn, Feand Co. For example, Sc may be selected to form Sc/Cu-BTC.

The present invention is further directed to new processes that use oneor more materials selected from a group including SMOF-7, m/Cu-BTC,where m=Sc, Ti, V, Mn, Fe and Co and m-MIL-100, where m=Sc, Ti and V.

SMOF-7 as an oxygen sorption material

SMOF-7 is a MOF material with tortuous porosity pathways and crystallinedefined pores. SMOF-7 has now been determined to have high selectivityfor O₂ over N₂. It is a crystalline metal-organic porous material withEu metal centers and TTB organic ligands. It has a 7×4.4 Å porediameter, an effective 5.1 Å pore opening and a specific surface area ofbetween 7-17 m²/g. SMOF-7 is Eu(TTB)(DEF)(H₂O).(DEF)₅, where TTB is 3,30,4,4 0-tetra (trimethylsilylethynyl)biphenyl, and DEF isN,N′-diethylformamide.

FIG. 1 is a SEM image of a single crystal of SMOF-7 synthesized inEXAMPLE 1, below. As can be seen in FIG. 1, the material crystallizes aslarge single crystals with plate-like morphology.

FIG. 2 is a ball-and-stick representation of the Eu-dimetal clustermolecular building block. As can be seen in FIG. 2, the Eu dimetalcluster is bridged by 6 TTB ligands: two bind in a chelate-bidentatemode, another two in a bridging bidentate fashion, while the remainingtwo adopt a bridging chelate-bidentate mode. Within this cluster, eachEu metal center has a 9-coordinate tricapped trigonal prismaticgeometry: eight of the available sites are coordinated by 4 independentTTB organic ligands, while the remaining coordination sphere iscompleted by one water and one DEF molecule per Eu metal center.

FIG. 3 is a view of the framework in SMOF-7. Hydrogen atoms have beenomitted for clarity. Atom color scheme: Eu=lighter gray; N=white;C=darker gray; and O=black As can be seen in FIG. 3, the dimetalclusters assemble to yield an extended three dimensional framework.

FIG. 4 illustrates novel (3,6)-connected net topography in SMOF-7. Ascan be seen in FIG. 4, this topology has not been previously observed inany materials to date. The dimetal cluster is represented as octahedralnode (grey), whereas the TTB linker is simplified as a 3-connected node(black). The short Schläfli (point) symbol for the net is{4.8²}2{4².8¹².10}.

FIG. 5 shows O₂ vs. N₂ sorption isotherm measured at 77 K in SMOF-7. Ascan be seen in FIG. 5, the SMOF-7 framework preferentially adsorbs O₂over N₂ at 77 K and up to 0.3 atm, with a separation value of 10.2.

SMOF-7 is synthesized by suspending a reaction mixture containing an Eumetal salt and a tritopic organic ligand in an organic solvent mixtureand heating the mixture to produce a crystalline phase with plate-likemorphology.

In an embodiment, SMOF-7 may be synthesized by mixing 1:3 or 1:2 molarratio of the Eu:TTB amounts of EuCl₃.6H2O and TTB(4,4′,4′-s-triazine-2,4,6-triyl-tribenzoic acid) ligand in a solventmixture of DMF (N,N-diethylformamide) and EtOH, capped and heated at115° C. for 1 day. The activated (desolvated) version of this phase hasan O₂/N₂ separation value of 10.2 at 77 K at 0.3 atm.

Example 1, Synthesis of SMOF-7

SMOF-7 was synthesized by forming a reaction mixture containingEuCl₃-6H2O (0.021 mmol, 8 mg), 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoicacid, (TTB) (0.043 mmol, 19 mg), N,N′-diethylformamide (DEF) (2 mL), andEtOH (3 mL) in a 20 mL scintillation vial. The vial was heated to 115°C. for 1 day at a rate of 1.5° C./min and cooled to room temperature ata cooling rate of 1° C./min. Plate-like crystalline SMOF-7 material wasobtained.

Technoeconomic analysis shows SMOF-7 exhibits preference for O₂ over N₂at 77K and had better predicted performance than common oxyfuel processzeolites (see Table 1).

TABLE 1 Performance of SNL SMOF-7 adsorbent and published performance ofzeolites (5A, CaX) for air separation. Metric Zeolites* SMOF-7Adsorption capacity (Saturation constant) 1.2,1.4 mol/kg 1.78 mol/kgSelectivity (Separation factor) 4.1, 11.2 10.2 Energy to produce 1 kg O2using PSA 0.28 kWh ~0.15 kWh *5A = Na₁₂[(AlO₂)₁₂(SiO₂)₁₂] • 27H₂O [3],CaX = (Ca₄₄)Si₁₀₄Al88O384 or if hydrated (Ca₄₄)(H₂O₂₂₀)Si₁₀₄Al₈₈O₃₈₄

Partially Substituted Cu-BTC (m/Cu-BTC).

Cu-BTC is a known MOF. Cu-BTC is a high surface area MOF (1500-2000m²/g) that consists of diatomic copper centers linked by1,3,5-benzenetricarboxylate units. Unsaturated meal centers (UMCs) areaccessible in the apical positions of the dimetal paddle wheel uponremoval of coordinated water with heat and vacuum.

According to an embodiment of the present disclosure, Cu-BTC ispartially substituted by one or more metals selected from a groupincluding Sc, Ti, V, Mn, Fe and Co for the Cu metal. Partiallysubstituted Cu-BTVC (m/Cu-BTC) has a stronger binding affinity to O₂ ascompared to Cu-BTC.

m/Cu-BTC (m=Sc, Ti, V, Mn, Fe and Co) is formed by adding a previouslysynthesized Cu-BTC to a stock solution of a substitute metal of interestin an organic solvent, and heated to produce a partially-exchanged orpartially substituted or mixed metal m/Cu-BTC.

Examples

Homogeneous substitution of Mn, Fe, and Co at various levels into Cu-BTCwere made to determine the performance of Mn and Co partialsubstitutions compared to Fe, and the effect of those substitutions onpreferential gas sorption were determined. Using a combination ofdensity functional theory (DFT) calculations, postsynthetic metalsubstitutions, materials characterization, and gas sorption testing, itwas demonstrate that the identity of the metal ion has a quantifiableeffect on their oxygen and nitrogen sorption properties at cryogenictemperatures. An excellent correlation is found between O₂/N₂selectivities determined experimentally at 77 K and the difference in O₂and N₂ binding energies calculated from DFT modeling data: Mn>Fe≈Co>>Cu.Room temperature gas sorption studies were also performed and correlatedwith metal substitution. The Fe exchanged sample shows a significantlyhigher nitrogen isosteric heat of adsorption at temperatures close toambient conditions (273-298 K) as compared to all other metals studied,indicative of favorable interactions between N₂ and coordinativelyunsaturated Fe metal centers. Interestingly, differences in gasadsorption results at cryogenic and room temperatures are evident; theyare explained by comparing experimental results with DFT bindingenergies (0 K) and room temperature Grand Canonical Monte Carlo (GCMC)simulations. Even more improved O₂ selectivity is shown for Sc, Ti and Vpartially substituted Cu-BTC.

Example 2, Synthesis of Mn-Exchanged Cu-BTC (Mn/Cu-BTC)

MnCl2-4H2O (0.098 g, 0.5 mmol) was dissolved in 3 MI ofN,N′-dimethylformamide (DMF). This solution was added to a solid sampleof pristine Cu-BTC (0.045 g, 0.2 mmol) and was heated to 90° C. in aconvection oven at a rate of 1.5° C./min, held at 90° C. for 1 day, andthen cooled to room temperature at a cooling rate of 1° C./min. Thesolvent was decanted, and the solid was washed with 5×10 mL of DMF.

Example 3, Synthesis of Fe-Exchanged Cu-BTC (Fe/Cu-BTC)

FeCl₂-4H₂O (0.045 g, 0.2 mmol) was dissolved in 3 mL of DMF. Thissolution was added to the pristine Cu-BTC (0.045 g, 0.2 mmol) and washeated to 90° C. in a convection oven at a rate of 1.5° C./min, held at90° C. for 1 day, and then cooled to room temperature at a cooling rateof 1° C./min. The solvent was decanted and the solid was washed with5×10 mL of DMF.

Example 4, Synthesis of Co-Exchanged Cu-BTC (Co/Cu-BTC)

CoCl₂.6H₂O (0.117 g, 0.5 mmol) was dissolved in 3 mL of DMF. Thissolution was added to the pristine Cu-BTC (0.045 g, 0.2 mmol), heated to90° C. in a convection oven at a rate of 1.5° C./min, held at 90° C. for1 day, and then cooled to room temperature at a cooling rate of 1°C./min. The solvent was decanted, and the solid was washed with 5×10 mLof DMF.

Sample Activation for Examples 2, 3 and 4 and Gas AdsorptionMeasurements.

Prior to measuring the gas adsorption isotherms, all samples wereactivated to generated porosity. The samples were activated by soakingin 15 mL of ethanol for 3 days, with the solvent replenished every 24 h.Subsequently, the samples were activated under a vacuum on aMicromeritics ASAP 2020 surface area and porosity analyzer, at 473 K for10 h.

Gas adsorption isotherms were measured using a Micromeritics ASAP 2020surface area and porosity analyzer. Nitrogen and oxygen gas of ultrahighpurity (99.999%, obtained from Matheson Tri-Gas) were used in theseexperiments. Gas adsorption isotherms at 77 K were measured in a liquidnitrogen dewar. Nitrogen and oxygen adsorption isotherms at 273, 283,and 298 K were measured in a dewar connected to a Polysciencecirculating isothermal bath with an advanced digital temperaturecontroller. Oxygen adsorption isotherms at 77 K were measured up to ˜0.2P/PO, since the saturation vapor pressure of O₂ at 77 K is 147.8 mmHg.

In the Examples above, the samples are porous, and the Langmuir surfaceareas were found to be 1586 m²/g for Co/Cu-BTC, 1773 m²/g for Fe/Cu-BTCand 1791 m²/g for Mn/Cu-BTC, which are all slightly lower than theLangmuir surface area for Cu-BTC, 2237 m²/g.

O₂ Sorption Processes

As discussed above, the disclosure is further directed to new O₂sorption processes. In an embodiment, the processes may use SMOF-7 andnewly disclosed, partially substituted and activated m/Cu-BTC (m=Sc, Ti,V, Mn, Fe and Co), including Mn/Cu-BTC, Fe/Cu-BTC Co/Cu-BTC, Sc/Cu-BTC,V/Cu-BTC and Ti/Cu-BTC to separate and release O₂ from a gas streamcontaining O₂.

In another embodiment, the processes may use m-MIL-100, where m=Sc, Tiand V. m-MIL-100 is a large pored MOF which can be synthesized directlyfrom reactants in different analogs by choosing different transitionmetals salts as the metal center. m-MIL-100 is metal-(1,3,5-BTC);BTC=Benzene-1,3,5-tricarboxylic acid; C₆H₃(CO₂H)₃; where m=Sc, Ti and V.

The MIL-100 framework is constructed from oxo-centered metal trimerslinked by benzenetricarboxylate (btc) ligands, forming tetrahedralcages, referred to as “supertetrahedra”. Corner-sharing of thesupertetrahedral building blocks defines a highly porous structure withtwo types of mesoporous cages of 25 Å and 29 Å in diameter, accessiblethrough pentagonal windows of 5.5 Å and hexagonal windows of ˜8.6 Å. Thecompositions have the general formula: metal-(1,3,5-BTC);BTC=Benzene-1,3,5-tricarboxylic acid; C₆H₃(CO₂H)₃, where metal isselected from the group consisting of Sc, Ti and V.

m-MIL-100 materials exhibit preferential oxygen sorption over nitrogenat temperatures from 77K-313 K. According to this disclosure, it issubmitted that the use of Sc, Ti and V in m-MIL-100 is shown to haveunexpectedly higher selectivity at lower temperatures compared to otherMOF materials. This allows for the use of these MOFs at/near ambientconditions for the selective removal of O₂ from air in such applicationsas, but not limited to medical production of O₂, on boardoxygen-generating systems, and oxyfuel combustion (high temperaturefurnace applications).

In an embodiment, m-MIL-100 is Sc-MIL-100. Synthesis and gas sorptiontesting of Sc-MIL-100 shows that Sc-MIL-100 exhibits high selectivityand capacity for O₂ over N₂ from 77 K through 313 K. Furthermore, it hashigher selectivity and capacity than a commercially available Fe-MIL-100analog.

Example 4, Synthesis of Sc-MIL-100

A mixture of Sc(NO₃)₃.xH₂O (0.02 g, 0.087 mmol) and1,3,5-benzenetricarboxylic acid (1,3,5-BTC, 0.018 g, 0.087 mmol) wasdissolved in 3 mL of N,N′-dimethylformamide (DMF) and concentrated HCl(37.0%, 1 drop). The solution was heated in a scintillation vial to 373K in a convection oven at a rate of 1.5 K/min, held at 373 K for 18hours, and then cooled to room temperature at a cooling rate of 1K/minute. The solvent was decanted and the solid was washed with 5×10 mLof DMF. The purity of the as synthesized compound was confirmed bypowder X-ray diffraction.

Experimental O₂ and N₂ gas sorption were obtained for Sc-MIL-100 over awide temperature range of 77, 258, 298, and 313 K, see FIGS. 6A-6D. Thedashed line in FIGS. 6A-6D represents the independent fit to theexperimental data for each temperature using a modified virial equation.The adsorption isotherms were measured on desolvated samples at 453 Kfor 12 hours. The Langmuir surface area for the Sc-MIL-100 wascalculated to be 1635 m²/g and is on par with previous reports. Aspredicted by GCMC simulations results, experiments show that O₂ is morefavorably adsorbed than N₂ at all temperatures studied. At 77 K, the Scmetal center has enhanced interactions with O₂ and results in higherloadings over N₂. This finding is consistent with our previous resultson pristine and metal exchanged Cu-BTC materials, also consisting ofuncoordinated metal centers. This trend is maintained at 258, 298, and313 K, temperatures relevant to energy efficient oxygen purificationprocesses, such as PSA.

Importantly, the structural integrity of the sample is preserved aftergas adsorption at these elevated temperatures, as evidenced by postanalyses XRD. Sc-MIL-100 is one of the few examples of MOF maintainingboth its structural integrity and a higher O₂ than N₂ capacity attemperatures well above room temperature. Apparently, theuncoordinated-metal center is not directly accessible in the 258 K-313 Krange, but presumably it still plays a role in preferred O₂ vs N₂adsorption, possibly from the puckered geometry of the oxo-centeredmetal trimer. One explanation is expanded opening into the tetrahedralcage due to the cupping of the trimer from an out of plane oxygendisplacement.

Isosteric heat of adsorption, Qst, provides important informationregarding the energetics between the adsorbed gas (O₂ or N₂) and theSc-MIL-100 framework. In order to calculate the Qst, each isotherm wasindependently fitted using a modified virial equation represented as adashed line in FIGUREES 6B-6D. Stronger binding affinities arecalculated for O₂=15.1 kJ/mol versus N₂=14.7 kJ/mol.

To assess the O₂/N₂ selectivity in conditions relevant to airseparations, a 20:80 mixture of O₂:N₂ was analyzed for feed pressures of0.1-1.0 bar, using the Ideal Adsorbed Solution Theory (IAST) for bothexperimental (see FIG. 7A) and GCMC isotherms. FIG. 7A shows calculated(IAST) O₂/N₂ selectivity for a 20:80 O₂/N₂ mixture from Sc-MIL-100experimental isotherms measured at 258, 298, and 313 K. (b) FIG. 7Bshows O₂ adsorption and desorption in Sc-MIL-100 over 10 cycles at 298 Kand 1 atm. Results indicate there is little variation in the O₂/N₂selectivity with total pressure. Importantly, the highest separationvalues are observed at 313K, O₂/N₂=1.5 suggesting great promise forincreased energy efficiency via realistic separation processes that donot rely on cryogenic cooling,

Further, the cycling performance of the Sc-MIL-100 sample was assessedat 298 K and 1 atm, see FIG. 7B. 10 consecutive adsorption-desorptioncycles were tested, with no additional degassing in between events. Nomeasurable loss to the O₂ adsorption capacity is noted over the rangestudied.

As a comparison to the Sc-MIL-100 sample, the O₂ and N₂ adsorptionisotherms were measured on a desolvated Fe-MIL-100 sample at 423 K for 6hours at 77, 258, 298, and 313 K, see FIG. 8A-8D.

The Langmuir surface area was calculated from the nitrogen adsorptionisotherm at 77 K and was found to be 1900 m²/g. This value is comparableto the surface area reported in the technical note by the commercialsource (2120 m2/g) though slightly lower than the one originallyreported by Horcajada et al. in Horcajada, P.; Surble, S.; Serre, C.;Hong, D.-Y.; Seo, Y.-K.; Chang, J.-S.; Greneche, J.-M.; Margiolaki, I.;Ferey, G. Synthesis and Catalytic Properties of MIL-100(Fe), anIron(III) Carboxylate with Large Pores. Chem. Commun. 2007, 2820-2822.These discrepancies might be related to distinct synthesis methods (theFe-MIL-100 studied here was based on a fluorine-free synthesis) and/orincomplete pore evacuation.

At 77 K, O₂ is more favorably adsorbed over N₂. At 258 K, Fe-MIL-100adsorbs slightly more N₂ than O₂, FIG. 8B. However, this is reversedagain as the temperature increases closer to ambient conditions, with O₂being adsorbed ˜20% more than N₂ at 298 K, FIG. 8c . At 313 K, theamount of adsorbed O₂ increases even more, ˜35% more than N₂, see FIG.8D.

In the Fe-MIL-100 sample, binding affinities for N₂ are stronger thanthose for O₂, Qst for N2=11.5 kJ/mol versus O₂ b=8.5 kJ/mol, FIG. 8e .The explanation for this is a different adsorption mechanism and/orbinding sites as compared to the Sc-MIL-100 sample. Similar to the Scanalogue, the Fe sample maintains structural integrity post testing at313 K, as shown by powder XRD.

The calculated IAST O₂/N₂ selectivity for the 20:80 O₂:N₂ mixture isconstant along the entire pressure range up to 1 bar, FIG. 8f . Uniqueto this framework, the O₂/N₂ selectivity increases as the temperatureincreases: O₂/N₂˜1 at 258 K, O₂/N₂=1.25 at 298 K, and reaching up toO₂/N₂=1.7 at 313 K.

As discussed above, the disclosed materials show high selectivity of O₂at ambient (298 K) or near ambient temperature (near ambient beingdefined herein as +/−5K (293 K to 303 K). As appreciated by one ofordinary skill in the art, sorption improves as temperature decreasesand pressure increases. Thus, at an initial adsorption temperature andpressure, desorption can be accomplished by either raising thetemperature, decreasing the pressure, or a combination of both. In anembodiment, the sorption temperature may be between 77 K and 313 K, andthe pressure range may be between 0.0001 atm and 1 atm. In anembodiment, the adsorption and desorption temperatures may be the same.Thus, for example, a PSA process according to an embodiment of thedisclosure may operate at ambient or near ambient temperatures, therebydecreasing energy cost in oxygen separations by avoiding cryogeniccrystallization of O₂ from air separations. Further in example,combustion processes can do separation at or near inlet gas feedtemperature and pressure for combustion process.

The processes include contacting one or more of the materials discussedabove with a gas stream containing O₂ to adsorb O₂ into the material.The material may be contained in a container, vessel or other enclosurethat is part of a system using purified or concentrated oxygen, such as,but not limited to a a PSA system, a TSA system, a personal and portablemedical oxygen supply system, an oxygen supply source for an oxyfuelcombustion system, and an on board oxygen generator (OBOG) system.

The gas is contacted and adsorbed by the material at an adsorptionpressure and temperature. The adsorption pressure is between 0.0001 atmand 10 atm. In an embodiment, the adsorption pressure is between 0.0001atm and 1 atm. In another embodiment, the adsorption pressure is between1 atm and 10 atm. In an embodiment, the adsorption and desorptionpressures are the same. The adsorption temperature is between 77 K and313 K. In an embodiment, the adsorption temperature is between 293 K and303 K. In another embodiment, the adsorption temperature is ambienttemperature.

Further according to the process, oxygen is released or desorbed fromthe material by lowering or decreasing the pressure to a desorptionpressure. In an embodiment, the pressure at which desorption occurs maybe the same as the adsorption pressure, or may be slightly higher orlower as would be appreciated by one of ordinary skill in the art.

The desorption pressure is between 0.0001 atm and 10 atm. In anembodiment, the desorption pressure is between 0.0001 atm and 1 atm. Inanother embodiment, the desorption pressure is between 1 atm and 10 atm.The desorption temperature is between 77 K and 313 K. In an embodiment,the desorption temperature is between 293 K and 303 K. In an embodiment,the desorption temperature is the same as the adsorption temperature. Inanother embodiment, the desorption temperature is ambient temperature.

The generated or released O₂ forms an oxygen supply stream that has anincreased concentration of O₂ compared to the initial gas stream. In anembodiment, the oxygen supply stream has an O₂ concentration greaterthan 95%. In an embodiment, the oxygen supply stream has an O₂concentration greater than 98%. In an embodiment, oxygen supply streamhas an O₂ concentration greater than 99.99.

In an embodiment, these materials may be used in pressure swingadsorption (PSA) methods for separating O₂ from air or another oxygencontaining gas streams.

The general operation or process steps of pressure swing adsorptionmethods are known, and need not be discussed in detail herein, as one ofordinary skill in the art would appreciated and understand incorporatingthe materials discussed above into such a process.

In another embodiment, the PSA process disclosed above may be used togenerate O₂ in an oxyfuel combustion system and process. It isappreciated that the systems and processes of oxyfuel combustion arewell known. In an embodiment, an oxyfuel combustion process according toan embodiment of the disclosure may operate at ambient or near ambienttemperatures.

Oxygen-enriched combustion and full oxy-fuel combustion processes arewell-known approaches to improve the heat transfer associated withstationary energy processes utilized by heavy industry or in powerproduction. The addition of oxygen results in higher thermal efficiency,greater flame stability, improved ignition characteristics, greaterburner turndown ratio, improved fuel flexibility, and reduced exhaustgas volumes, all stemming from the reduction or elimination of the N₂component of air. In addition, NO_(x) emissions can be nearly completelyeliminated in oxy-fuel combustion. Finally, oxy-fuel combustion offers alower-cost route to CO₂ capture, for either subsequent utilization (suchas in enhanced oil recovery) or geologic sequestration. While theglass-melting industry, aluminum industry, and steel-making industryhave adopted oxy-fuel combustion into some of their operations, itsoverall penetration into industrial and power markets is currentlyconstrained by the high cost of existing air separation technologies forgenerating oxygen.

A major advantage of oxy-fuel combustion to thermal processes is throughthe much greater radiant emission from these flames. The radiantemission increases because of the higher flame temperatures associatedwith oxygen-enrichment (up to nearly 3000 K) and because the flame gasesthemselves have a much greater emissivity—absent the dilution from N₂associated with traditional air-based combustion, the concentrations ofradiantly active combustion products are 3.5 times larger in oxy-fuelflames. Careful tailoring of oxy-fuel flames allows the formation ofenhanced soot levels within the flame, increasing thermal radiation(while still burning out soot and avoiding soot emissions). Radiationhas been shown to cause 98% of the heat transfer from oxy-fuel flames tothe ‘batch’ in glass-melting furnaces. Improvements in furnaceefficiency when retrofitting air-fired furnaces to oxy-fired have rangedfrom 20-60% in glass and steel heating furnaces. The disclosed materialsare the cutting edge materials needed for dramatic improvements tooxy-fuel combustion.

In another embodiment, the materials disclosed above may be used in onboard oxygen generators (OBOGs). It is appreciated that the systems andprocesses of OBOGs are well known. In an embodiment, an on board oxygengenerator process according to an embodiment of the disclosure mayoperate at ambient or near ambient temperatures.

Although the invention has been described in detail with particularreference to these preferred embodiments, other embodiments can achievethe same results. Variations and modifications of the present inventionwill be obvious to those skilled in the art and it is intended to coverin the appended claims all such modifications and equivalents. Theentire disclosures of all references, applications, patents, andpublications cited above are hereby incorporated by reference.

What is claimed is:
 1. A composition, comprising: a metal-organicframework material capable of oxygen capture, the metal organicframework material consisting essentially of m/Cu-BTC, whereBTC=benzene-1,3,5-tricarboxylic acid and m/Cu represents partialsubstitution of Cu with a metal ion (m) selected from a group consistingSc, Ti, V, Mn, Fe and Co.
 2. The composition of claim 1, wherein m isSc.
 3. A process, comprising: contacting a gas stream containing oxygenat a first concentration with a metal-organic framework material havingthe formula m/Cu-BTC, where BTC=benzene-1,3,5-tricarboxylic acid andm/Cu represents partial substitution of Cu with a metal ion (m) selectedfrom a group consisting Sc, Ti, V, Mn, Fe and Co at a first temperatureand first pressure to adsorb oxygen from the gas stream into themetal-organic framework; and desorbing oxygen from the metal-organicframework material at a second temperature and a second pressure.
 4. Theprocess of claim 3, wherein the first and second temperatures are equal.5. The process of claim 3, wherein the second pressure is less than thefirst pressure.
 6. The process of claim 3, wherein the secondtemperature is greater than the first temperature.
 7. The process ofclaim 3, wherein the first temperature is ambient temperature.